CN109954412A - A kind of load has Ti3+-TiO2/SiO2PES ultrafiltration membrane of nano wire and its preparation method and application - Google Patents
A kind of load has Ti3+-TiO2/SiO2PES ultrafiltration membrane of nano wire and its preparation method and application Download PDFInfo
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- CN109954412A CN109954412A CN201910169790.9A CN201910169790A CN109954412A CN 109954412 A CN109954412 A CN 109954412A CN 201910169790 A CN201910169790 A CN 201910169790A CN 109954412 A CN109954412 A CN 109954412A
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- sio
- tio
- ultrafiltration membrane
- nano wire
- pes ultrafiltration
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- 239000012528 membrane Substances 0.000 title claims abstract description 121
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 97
- 239000002070 nanowire Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 101
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 101
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 101
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 101
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 101
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 11
- 239000004695 Polyether sulfone Substances 0.000 claims description 89
- 229920006393 polyether sulfone Polymers 0.000 claims description 89
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000008363 phosphate buffer Substances 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 7
- 239000002253 acid Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 13
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 18
- 229960000907 methylthioninium chloride Drugs 0.000 description 18
- 238000012360 testing method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of loads Ti3+‑TiO2/SiO2The PES ultrafiltration membrane of nano wire, PES ultrafiltration membrane is by the polymerization of dopamine, by a certain amount of Ti3+‑TiO2/SiO2It is nanowire supported in PES ultrafiltration membrane surface.The invention also discloses above-mentioned load Ti3+‑TiO2/SiO2The preparation method and application of the PES ultrafiltration membrane of nano wire.The present invention loads Ti3+‑TiO2/SiO2The water contact angle of the PES ultrafiltration membrane of nano wire becomes smaller, and hydrophilicity is remarkably reinforced；Under the conditions of radiation of visible light, the Ti of film surface load3+‑TiO2/SiO2Nano wire can degrade the pollutant of PES ultrafiltration membrane surface, reduce blocking of the film surface pollutant to fenestra, load is made to have Ti3+‑TiO2/SiO2The PES ultrafiltration membrane antifouling property of nano wire is remarkably reinforced, so that membrane flux increases, rejection is improved.
Description
Technical field
The present invention relates to a kind of loads Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire, further relating to above-mentioned load has Ti3 +-TiO2/SiO2The preparation method of nano wire PES ultrafiltration membrane and the PES ultrafiltration membrane dyestuff in separation, filtering, degraded solutions
The application of aspect belongs to filtering technical field of membrane.
Background technique
Dyestuff is widely used in the industry such as weaving, papermaking and printing as a kind of large chemical industrial product.In recent years,
With the rapid development of this kind of industry, the usage amount of all kinds of dyestuffs is growing day by day, expedites the emergence of a large amount of waste water from dyestuff.Waste water from dyestuff is general
Have the characteristics that toxicity is big, color is deep, difficult for biological degradation, thus water environment protection to China and improvement bring it is unprecedented
Test.
Polyether sulfone (PES) has good mechanical performance and anticorrosive acid-proof alkaline, when operation is run, has chemistry
The advantages that low energy consumption, high-efficient is a kind of excellent membrane material.Membrane separation technique is one of new and high technology, is efficiently applied to crowd
It is multi-field, produce huge economic benefit and social benefit.Membrane separation technique has many advantages, such as chemistry, and low energy consumption, high-efficient,
But fouling membrane can reduce the process performance of film, limit the development and application of membrane separation technique, thus to need poly (ether-sulfone) ultrafiltration membrane into
Row surface is modified.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide a kind of loads Ti3+-TiO2/SiO2Nano wire
PES ultrafiltration membrane, the PES ultrafiltration membrane can centainly operation pressure difference under carry out dyestuff the degradation for efficiently separating and polluting, and
Also there is strong contamination resistance.
The present invention also technical problems to be solved, which are to provide above-mentioned load, Ti3+-TiO2/SiO2The PES ultrafiltration of nano wire
The preparation method of film.
The last technical problems to be solved of the present invention, which are to provide above-mentioned load, Ti3+-TiO2/SiO2The PES of nano wire is super
Application of the filter membrane in separation, filtering, degraded solutions in terms of dyestuff.
In order to solve the above technical problems, the technical scheme adopted by the invention is as follows:
A kind of load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire, the PES ultrafiltration membrane surface load have certain
The Ti of amount3+-TiO2/SiO2Nano wire.
Wherein, Ti3+-TiO2/SiO2Nano wire is carried on PES ultrafiltration membrane surface by dopamine.
Above-mentioned load has Ti3+-TiO2/SiO2PES ultrafiltration membrane is immersed in molten by the preparation method of the PES ultrafiltration membrane of nano wire
There is Ti3+-TiO2/SiO2In the phosphate buffer of nano wire and dopamine, obtaining film surface load has Ti3+-TiO2/SiO2Nanometer
The PES ultrafiltration membrane of line.
Above-mentioned load has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, specifically comprises the following steps:
Step 1, PES ultrafiltration membrane is prepared；
Step 2, T is preparedi3+-TiO2/SiO2Nano wire；
Step 3, preparation load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire: by Ti made from step 23+-TiO2/
SiO2Nano wire and dopamine are added in phosphate buffer, and PES ultrafiltration membrane made from step 1 is then immersed in above-mentioned phosphoric acid
In buffer, haptoreaction for a period of time after, take out PES ultrafiltration membrane, film surface load is obtained after dry Ti3+-TiO2/SiO2
The PES ultrafiltration membrane of nano wire.
Wherein, in step 1, PES ultrafiltration membrane is specifically prepared in the following way: by the desired amount of polyether sulfone and poly- second
Alkene pyrrolidone is dissolved in n,N-dimethylacetamide solvent, stirs to get casting solution；It is evenly applied to after casting solution is deaerated
Glass pane surface is coated with the smooth conversion for carrying out phase into the water of glass plate of casting solution, obtains PES ultrafiltration after standing
Film.
Wherein, in step 2, Ti3+-TiO2/SiO2Nano wire is specifically prepared in the following way: by required volume ratio
Butyl titanate, ethyl alcohol and acetylacetone,2,4-pentanedione mixing, obtain mixed liquor A；By a certain amount of ethyl orthosilicate, deionized water, ammonia
Water and dehydrated alcohol mixing, obtain mixed liquid B；Mixed liquor A and mixed liquid B are persistently stirred a period of time, after being reacted under high temperature
It is calcined again, obtains TiO2/SiO2Nano particle；By TiO2/SiO2Nano particle pours into the NaOH solution of certain solubility,
TiO is obtained after reaction2/SiO2Nano wire；By TiO2/SiO2Nano wire and NaBH4Ground and mixed, when reacting one section in argon gas
Between, obtain Ti3+-TiO2/SiO2Nano wire.
Wherein, in step 3, in phosphate buffer, the concentration of phosphate buffer is 10mM, Ti3+-TiO2/SiO2Nano wire
Mass fraction be 0.005%, the mass fraction of dopamine is 0.01%, and the haptoreaction time is 16~for 24 hours.Pass through dopamine
Polymerization by Ti3+-TiO2/SiO2It is nanowire supported in PES ultrafiltration membrane surface.
Wherein, phase conversion time is for 24 hours.
Wherein, time mixed liquor A and mixed liquid B persistently stirred is 60~80min, the reaction temperature reacted under high temperature
It is 180 DEG C, reaction time 10h, the temperature calcined after reaction is 550 DEG C, calcination time 2h；By TiO2/SiO2Nano particle
Pouring into the reaction temperature reacted in the NaOH solution of certain solubility is 180 DEG C, reaction time 48h, NaOH solution it is dense
Degree is 10M；By TiO2/SiO2Nano wire and NaBH4Mixed grinding, the reaction temperature reacted in argon gas are 350 DEG C, when reaction
Between be 1h.
Above-mentioned load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire dyestuff side in separation, filtering, degraded solutions
The application in face.Wherein, the dyestuff is methylene blue.
Compared with the prior art, it is had the beneficial effect that possessed by technical solution of the present invention
Present invention load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire has Ti due to film surface3+-TiO2/SiO2
Nano wire catalysis material, therefore the water contact angle of ultrafiltration membrane becomes smaller, the increased hydrophilicity of film is conducive to decelerating membrane pollution, increases
Membrane flux；In addition under visible light illumination, the Ti of film surface3+-TiO2/SiO2The nano wire catalysis material PES that can degrade is super
The pollutant of filter membrane surface, so that further decelerating membrane pollution, increases membrane flux；Present invention load has Ti3+-TiO2/SiO2It receives
The PES ultrafiltration membrane of rice noodles has good separating and filtering and degradation effect to methylene blue dye.
Detailed description of the invention
Fig. 1 is that present invention load has Ti3+-TiO2/SiO2The process flow chart of the PES ultrafiltration membrane of nano wire；
Fig. 2 is that present invention load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire carries out methylene blue solution membrane flux
With the experimental rig figure of methylene blue solution rejection；
Fig. 3 is that present invention load has Ti3+-TiO2/SiO2The electron microscope of the PES ultrafiltration membrane surface of nano wire；
Fig. 4 is that present invention load has Ti3+-TiO2/SiO2The electron microscope of the PES ultrafiltration membrane cross section of nano wire；
Fig. 5 is that present invention load has Ti3+-TiO2/SiO2The XPS of the PES ultrafiltration membrane cross section of nano wire schemes；
Fig. 6 is that present invention load has Ti3+-TiO2/SiO2The UV-vis of the PES ultrafiltration membrane cross section of nano wire schemes.
Specific embodiment
Below in conjunction with attached drawing, technical scheme is described further, but the scope of protection of present invention is simultaneously
It is not limited to this.
Embodiment 1
Present invention load has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, specifically includes following step
It is rapid:
Step 1, it prepares PES ultrafiltration membrane: 8g polyether sulfone and 1g polyvinylpyrrolidone is added to 43.5mL N, N- diformazan
In yl acetamide solvent, sealing stirring for 24 hours, obtains casting solution at room temperature；Casting solution is placed in the 6h that deaerates at room temperature, it then will be big
The casting solution of about 15mL on a glass, with scraping hymenotome on a glass with 0.5cm/s at the uniform velocity knifing；It is coated with casting solution
Glass plate it is smooth be put into deionized water carry out phase conversion, PES ultrafiltration membrane is obtained after for 24 hours；Load has Ti3+-TiO2/
SiO2The aperture of the PES ultrafiltration membrane of nano wire is 12nm；
Step 2: preparation Ti3+-TiO2/SiO2Nano wire: by 17ml butyl titanate, 50ml ethyl alcohol and 5mL acetylacetone,2,4-pentanedione
Mixing, stirring 1h obtain mixed liquor A；By 2.25mL ethyl orthosilicate, 10mL deionized water, 20mL ammonium hydroxide and 20mL dehydrated alcohol
Mixing, stirring 1h obtain mixed liquid B；Mixed liquor A and mixed liquid B are mixed, 1h is persistently stirred and obtains mixed liquor C, by mixed liquor C
It is placed in reaction kettle, reacts 10h under 180 degree, obtained product is ground, be centrifuged after grinding with dehydrated alcohol and deionized water
Washing 2 times, calcines 2h in 550 degree of tube furnaces for the product after washing, obtains TiO2/SiO2Nano particle；By 0.4gTiO2/
SiO2Nano particle pours into the NaOH solution that 60mL concentration is 10M, reacts 48h in 180 degree reaction kettle, obtains TiO2/SiO2
Nano wire；By 0.2gTiO2/SiO2Nano wire and 0.4gNaBH4Mixed grinding leads to argon gas in tube furnace, in 350 degree of lower calcinings
60min obtains Ti3+-TiO2/SiO2Nano wire.
Step 3, preparation load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire: by 20mg Ti3+-TiO2/SiO2It receives
Rice noodles and 40mg dopamine are added in the phosphate buffer that 40mL concentration is 10mM, are then immersed in PES ultrafiltration membrane above-mentioned
In phosphate buffer, haptoreaction for 24 hours, takes out PES ultrafiltration membrane, obtaining film surface load after 60 degree of lower dryings has Ti3+-TiO2/
SiO2The PES ultrafiltration membrane of nano wire.Ti on PES ultrafiltration membrane3+-TiO2/SiO2The load capacity of nano wire is 10mg.
There is Ti to load made from embodiment 13+-TiO2/SiO2The PES ultrafiltration membrane of nano wire is filled with experiment shown in Fig. 2
Set the testing experiment for carrying out methylene blue solution membrane flux and methylene blue separating effect:
Taking initial concentration is the methylene blue solution 1L of 10mg/L, has Ti to load in embodiment 13+-TiO2/SiO2Nanometer
The PES ultrafiltration membrane and PES ultrafiltration membrane of line carry out film methylene blue solution water flux respectively in experimental provision and methylene blue is molten
The testing experiment of liquid rejection, wherein the diameter of PES ultrafiltration membrane is 5cm, and it is 0.22MPa that diaphragm pump, which provides operating pressure, is being had
It is tested respectively in the case of illumination and no light, each testing time is 120min.Methylene blue solution water flux calculation formula isWherein J1For the water flux of methylene blue solution, unit Lm-2·h-1, Q1Film water body is crossed for methylene blue solution
Product, unit m3；Methylene blue solution rejection Rejection isWherein CpFor percolate
Concentration, CfIt (is changed over time) for methylene blue solution concentration, methylene blue concentration spectrophotometer measurement.Test experiments knot
Fruit sees Tables 1 and 2.
Table 1 is that the load obtained of embodiment 1 has Ti3+-TiO2/SiO2The PES ultrafiltration membrane and PES ultrafiltration membrane of nano wire are to Asia
Comparison of the methyl blue membrane flux in the case where there is non-illuminated conditions:
Table 2 is that the load obtained of embodiment 1 has Ti3+-TiO2/SiO2The PES ultrafiltration membrane and PES ultrafiltration membrane of nano wire are to Asia
Comparison of the methyl blue solution rejection in the case where there is non-illuminated conditions:
| Rejection R% | |
| Embodiment 1 (no light) | 88 |
| Embodiment 1 (visible light) | 89 |
| PES ultrafiltration membrane (no light) | 96 |
| PES ultrafiltration membrane (visible light) | 98 |
。
As shown in Table 1, after running 120min under visible light, load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire
Methylene blue solution membrane flux is improved under visible light.This is because under visible light illumination condition, film surface load
Ti3+-TiO2/SiO2Nano wire generates electrons and holes causes the pollutant of film surface to occur to generate strong oxidative free radical
Light degradation, makes fouling membrane have certain alleviation, so that methylene blue solution membrane flux is risen.It is produced by the present invention negative
It is loaded with Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire couples UF membrane with catalysis material, can be effective from many aspects
Decelerating membrane pollution problem (load Ti3+-TiO2/SiO2On the one hand nano wire can increase the hydrophilicity of PES ultrafiltration membrane, another party
Face, which can degrade, is deposited on the pollutant of PES ultrafiltration membrane surface), thus increase membrane flux, decelerating membrane pollution.
As shown in Table 2, under the conditions of radiation of visible light, load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire is to dirt
The rejection for contaminating object rises, this is because pollutant is by photocatalytic degradation at inorganic matter.In addition, in no light, load
There is Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire is because of Ti3+-TiO2/SiO2The load of nano wire subtracts PES ultrafiltration membrane aperture
Small, porosity increases, so load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane rejection ratio PES ultrafiltration membrane of nano wire is high.
As shown in Fig. 2, the experimental provision belongs to cross-flow filtration, while belonging to photocatalysis membrana separation coupling reactor.Storage
Sink Methylene Blue solution is delivered in homemade membrane reactor by diaphragm pump, is visible light source, warp above membrane reactor
A part of solution of membrane reactor is crossed to be back in water storage tank through pipeline, formed pollutant that circulation deposits ultrafiltration membrane film surface into
Row sluicing；Another part then passes through ultrafiltration membrance filter into percolate cup, by day flushconnection computer automatic weighing penetrating fluid
Volume.
As shown in figure 3, Ti3+-TiO2/SiO2It is nanowire supported in PES ultrafiltration membrane surface, relative to nano particle, nanometer
Line reduces the blocking to fenestra.As shown in figure 4, load TiO2/SiO2The PES ultrafiltration membrane of nano wire has porous support layer and cause
Close separating layer.As shown in figure 5, Ti3+-TiO2/SiO2Two main peaks of the nano wire on the position Ti 2p3/2 and Ti 2p1/2 can
To be fitted to four peaks, wherein the peak value of 458.55eV and 464.48eV is respectively from Ti4+2p3/2 and Ti4+2p1/2, and
The peak value of 457.83eV and 463.54eV is respectively Ti3+2p3/2 and Ti3+2p1/2, to demonstrate Ti3+Presence, hydroboration
Sodium plays the role of reduction.As shown in fig. 6, Ti3+-TiO2/SiO2Nano wire is not only inhaled in ultraviolet region with stronger optics
Receipts ability, and also there is stronger optical absorption ability in visible light region.
The present invention loads Ti3+-TiO2/SiO2The water contact angle of the PES ultrafiltration membrane of nano wire becomes smaller, and hydrophilicity obviously increases
By force；Under the conditions of radiation of visible light, the Ti of film surface load3+-TiO2/SiO2Nano wire can degrade PES ultrafiltration membrane surface
Pollutant reduces blocking of the film surface pollutant to fenestra, load is made to have Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire is anti-
Pollutant performance is remarkably reinforced, so that membrane flux increases, rejection is improved.
Claims (10)
1. a kind of load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire, it is characterised in that: the PES ultrafiltration membrane surface is negative
It is loaded with a certain amount of Ti3+-TiO2/SiO2Nano wire.
2. load according to claim 1 has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire, it is characterised in that: Ti3+-
TiO2/SiO2Nano wire is carried on PES ultrafiltration membrane surface by dopamine.
3. load as claimed in claim 2 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature exist
In: PES ultrafiltration membrane is immersed in dissolved with Ti3+-TiO2/SiO2In the phosphate buffer of nano wire and dopamine, film surface is obtained
Load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire.
4. load according to claim 3 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
It is, specifically comprises the following steps:
Step 1, PES ultrafiltration membrane is prepared；
Step 2, T is preparedi3+-TiO2/SiO2Nano wire；
Step 3, preparation load has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire: by Ti made from step 23+-TiO2/SiO2
Nano wire and dopamine are added in phosphate buffer, and PES ultrafiltration membrane made from step 1 is then immersed in above-mentioned phosphoric acid buffer
In liquid, haptoreaction for a period of time after, take out PES ultrafiltration membrane, film surface load is obtained after dry Ti3+-TiO2/SiO2Nanometer
The PES ultrafiltration membrane of line.
5. load according to claim 4 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
Be: in step 1, PES ultrafiltration membrane is specifically prepared in the following way: by the desired amount of polyether sulfone and polyvinylpyrrolidine
Ketone is dissolved in n,N-dimethylacetamide solvent, stirs to get casting solution；Glass plate table is evenly applied to after casting solution is deaerated
Face is coated with the smooth conversion for carrying out phase into the water of glass plate of casting solution, obtains PES ultrafiltration membrane after standing.
6. load according to claim 4 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
It is: in step 2, Ti3+-TiO2/SiO2Nano wire is specifically prepared in the following way: by the metatitanic acid four of required volume ratio
Butyl ester, ethyl alcohol and acetylacetone,2,4-pentanedione mixing, obtain mixed liquor A；By a certain amount of ethyl orthosilicate, deionized water, ammonium hydroxide and anhydrous
Ethyl alcohol mixing, obtains mixed liquid B；Mixed liquor A and mixed liquid B are persistently stirred a period of time, forged again after being reacted under high temperature
It burns, obtains TiO2/SiO2Nano particle；By TiO2/SiO2Nano particle pours into the NaOH solution of certain solubility, after reaction
To TiO2/SiO2Nano wire；By TiO2/SiO2Nano wire and NaBH4Mixed grinding reacts a period of time in argon gas, obtains Ti3 +-TiO2/SiO2Nano wire.
7. load according to claim 4 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
Be: in step 3, in phosphate buffer, the concentration of phosphate buffer is 10mM, Ti3+-TiO2/SiO2The quality of nano wire point
Number is 0.005%, and the mass fraction of dopamine is 0.01%, the haptoreaction time is 16~for 24 hours.
8. load according to claim 5 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
Be: phase conversion time is for 24 hours.
9. load according to claim 6 has Ti3+-TiO2/SiO2The preparation method of the PES ultrafiltration membrane of nano wire, feature
Be: the time that mixed liquor A and mixed liquid B are persistently stirred is 60~80min, and the reaction temperature reacted under high temperature is 180 DEG C,
Reaction time is 10h, and the temperature calcined after reaction is 550 DEG C, calcination time 2h；By TiO2/SiO2Nano particle pours into centainly
The reaction temperature reacted in the NaOH solution of solubility is 180 DEG C, reaction time 48h, and the concentration of NaOH solution is 10M；
By TiO2/SiO2Nano wire and NaBH4Mixed grinding, the reaction temperature reacted in argon gas are 350 DEG C, reaction time 1h.
10. load described in claim 1 has Ti3+-TiO2/SiO2The PES ultrafiltration membrane of nano wire is in separation, filtering, degraded solutions
Application in terms of middle dyestuff.
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